Transition metal oxide, which undergoes a conversion reaction in the negative electrode material for a lithium-ion batteries, has a high specific capacity, but still has several critical problems. In this study, manganese pyrophosphate (Mn2P2O7), nickel pyrophosphate (Ni2P2O7), and carbon composite materials with pyrophosphates as novel negative electrode materials instead of transition metal oxide, are synthesized through simple solid-state reaction. The initial reversible capacity of Mn2P2O7 and Ni2P2O7 are 333 and 340 mAh g-1, and when the composite materials are composed with carbon, the reversible capacity increases to 433 and 387 mAh g-1, respectively. The initial Coulombic efficiency is also improved by about 10%. The Mn2P2O7 and carbon composite material has the highest initial capacity and efficiency, and has the best cycle performance. Mn2P2O7 containing polyanion, has a lower specific capacity due to the large mass of polyanion compared to MnO (manganese oxide). However, since Mn2P2O7 shows a voltage curve with a slope, the charging (lithiation) voltage increases from 0.51 to 0.57 V (vs. Li/Li+), and the discharge (delithiation) voltage decreases from 1.15 to 1.01 V (vs. Li/Li+). Therefore, the voltage efficiency of the cell is improved because the voltage difference between charging and discharging is greatly reduced from 0.64 to 0.44 V, and the operating voltage of the full cell increases because the negative electrode potential is lowered during the discharging process.